Esters of oxypropylated aromatic amines and polycarboxylic acids



cal.

United States Patent ESTERS 0F OXYPROPYLATED AROMATIC AMlN ES AND POLYCARBOXYLIC ACIDS Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, a corporation of Delaware No Drawing. Application January 9, 1952, Serial No. 265,711

8 Claims. (Cl. 260-475) The present invention is concerned with certain new chemical products, compounds or compositions which have useful application in various arts.

The particular compounds subsequently described herein in greater detail are hydrophile synthetic products, and more particularly, fractional esters obtained from polycarboxy acids and nitrogen-containing diols obtained by the oxypropylation of a primary amine having not more than 7 carbon atoms and containing a phenyl radi- For all practical purposes this limits the amine to aniline, benzylamine, and a toluidine, such as orthotoluidine. Furthermore, the dihydroxylated compound prior to esterification must be water-insoluble and kerosenesoluble. Momentarily ignoring certain variants of structure which will be considered subsequently the hydrophile synthetic products may be exemplified by the following formula:

0 (HO O C)n"R (OHDCQ)II 1TI (CBHBO)IV R(C O OH)" R! in which R is the phenyl radical, the methylphenyl radical, or the benzyl radical, and n and n are whole numbers with the proviso that it plus n equals a sum varying from to 80; n" is a whole number not over 2 and R is the radical of the polycarboxy acid COOH (OOOH)"" and preferably free from any radicals having more than 8 uninterrupted carbon atoms in a single group, and with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble and kerosenesoluble.

The products of this invention are of particular value for resolving pertroleum emulsions of the water-in-oil type that are commonly referred to as cut oil," roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This use of the particular products described herein is described and claimed in my copending application Serial 'a No. 183,294, filed September 5, 1950, and now abandoned.

The products are also useful for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities particularly inorganic salts from pipeline oil.

The cheapest of the three amines which can be employed in aniline and this my preferred reagent. The oxypropylation of aniline is well known although I am not aware that aniline (or for that matter a toluidine or benzylamine) has ever been oxyalkylated with propylene oxide so as to yield a product which is water-insoluble I and kerosene-soluble.

For convenience, what is said hereinafter will be divided into four parts:

Part 1 is concerned with the preparation of the oxypropylation derivatives of the specified amines;

Part 2 is concerned with the preparation of the esters from the oxypropylated derivatives;

Part 3 is concerned with the structure of the oxypropylation products obtained from the specified amines. Insofar that such materials are dihydroxylated there is a relationship to ordinary diols which do not contain a ice nitrogen atom, all of which is considered briefly in this particular part: and

Part 4 is concerned with certain derivatives which can be obtained from the oxypropylated primary amines. In some instances such derivatives are obtained by modest oxyethylation preceding the oxypropylation step, or oxypropylation followed by oxyethylation. This results in diols having somewhat difierent properties which can then be reacted with the same polycarboxy acids or anhydrides described in Part 2.

PART 1 Oxypropylation, like other oxyalkylation operations, should be carried out with due care, in equipment specially designed for the purpose and with precautions that are now reasonably well understood. Reference is made to the discussion of the factors involved in oxypropylation which appears in Patent 2,626,918, column 5 through column 8, the considerations and the technique there discussed being equally applicable to the production of the compounds of the present application. In view of this reference to Patent 2,626,918, no general discussion of the factors involved in oxypropylation is given here, and the procedure will simply be illustrated by the following examples:

Example In The starting material was a commercial grade of aniline. The particular autoclave employed was one with a capacity of 15 gallons, or on the average of about pounds of reaction mass. The speed of the stirrer could be varied from to 350 R. P. M. 5 pounds of aniline were charged into the autoclave along with one-half pound caustic soda. The reaction pot was flushed out with nitrogen. The autoclave was sealed and the automatic devices adjusted and set for injecting a total of 65.25 pounds of propylene oxide in approximately a 10-hour period. The pressure regulator was set for a maximum of 35 pounds per square inch. This meant that the bulk of the reaction could take place, and probably did take place, at a lower pressure. This comparatively low pressure was the result of the fact that considerable catalyst was present, and especially when one allows for the fact that aniline does have some basicity itself. The propylene oxide was added comparatively slowly, and, more important, the selected temperature range was 205 to 215 F. (about the boiling point of water). The initial introduction of propylene oxide was not started until the heating devices had raised the temperature to about the boiling point of water. At the completion of the reaction a sample was taken and oxypropylation proceeded as in Example 2a, immediately succeeding.

Example 2a 53.4 pounds of the reaction mass identified as Example la, preceding, were permitted to remain in the reaction vessel and without the addition to any more catalyst 17.25 pounds of propylene oxide were added. The oxypropylation was conducted in substantially the same manner with regard to pressure and temperature as in Example la, preceding, except that the reaction was complete in slightly less time, i. e., 8 hours instead of 10 hours. At the end of the reaction period part of the sample was withdrawn and oxypropylation was continued as described in Example 3a, following.

Example 3a 62.6 pounds of the reaction mass identified as Example 2a, preceding, was permitted to remain in the reaction vessel. 27.75 pounds of propylene oxide were introduced in this third stage. No additional catalyst was added. The time period required was the same as in Example 20, preceding, i. e., 8 hours. The conditions of reaction as far as temperature and pressure were concerned were substantially the same as in Example 1a, preceding. At the completion of the reaction part of the reaction mass was withdrawn and the remainder subjected to oxypropylation as described in Example 4a, following.

Example 4a 66.4 pounds of the reaction mass: identified as Example 3a, preceding, Were permitted to remain in the autoclave. Without adding any more catalyst this was subjected to further oxypropylation as in the preceding example. The amount of propylene oxide added was 34.75 pounds. This was introduced in a 10-hour period. Conditions in regard to temperature and pressure were substantially the same as in Example In, preceding. At the end of the reaction period part of the sample was withdrawn and the remainder of the reaction mass was subjected agam to further oxypropylation as described in Example 5a, following.

Example 5a Approximately 74.4 pounds of the reaction mass identified as Example 4a, preceding, was permitted to stay in the autoclave. No additional catalyst was introduced. 14.0 pounds of propylene oxide were added. The time required to add this propylene oxide was 9 hours. The conditions of reaction in regard to temperature and pressure were substantially the same as in Example 1a, precedln this particular series of examples the oxypropylation was stopped at this stage. In other series I have continued the oxypropylation so that the theoretical molecular weight varied from 6,000 to 7,000 but the increase in molecular weight by hydroxyl determination Was comparatively small, being 2300 in the first case and 2360 in the second case.

What is said herein is presented in tabular form in Table 1 immediately following, with some added 1n formation as to molecular weight and as to solubility of be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of common knowledge and requires no further elaboration. Infact, it is illustrated by some of the examples appearing in the patent previously mentioned.

PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated derivatives described in Part 1, immediately preceding, and polycarboxy acids, particularly dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or anhydride adducts as obtained by the Diels-Alder reaction from reactants such as maleic anhydride and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification. They may contain as many as 36 carbon atoms as, for example, the acids obtained by dimerization of unsaturated fatty acids, unsaturated monocarboxy fatty acids, or unsaturated monocarboxy acids having 18 carbon atoms. Reference to the acid in the hereto appended claims obviously includes the anhydrides or any other obvious equivalents. My preference, however, is to use polycarboxy acids having not over 8 carbon atoms.

The production of esters including acid esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds is well known. Needless to say, various compounds may be used such as the low the reaction product in water, xylene and kerosene. molal ester, the anhydride, the acyl chloride, etc. How- TABLE 1 O 't' before Composition at end omposl 10D bM'hWa Max Max. T

Y y pres. ime Amine Oxide Cata- Theo. Amine Oxide Catadeteri g lb h amt amt., lyst, mol. amt., amt., lyst, min. sq. In.

lbs. lbs. lbs. wt. lbs. lbs. lbs.

5 0 0 50 1,305 5. 00 65. 25 0. 50 1, 276 205-215 10 3 76 49. 24 0 37 1, 740 3. 76 66. 49 O. 37 1, 596 205-215 35 8 3 33 58. 96 0. 33 2, 515 3. 33 86. 71 O. 33 1, 744 205215 35 8 2 63. 67 O. 25 3, 820 2. 45 98. 42 0. 25 2, 208 205-215 35 10 1 8O 72. 40 0 17 4, 560 1. 80 86. 49 0. 17 2, 720 205-215 25 9 All examples (la through 5a) were insoluble in water, but soluble in xylene and soluble in kerosene. This was true, also, of other samples in which the theoretical molecular weight was somewhat higher as in the instance of those examples whose theoretical molecular weight was in the 6,000 to 7,000 range.

This applied also to samples obtained in substantially the same manner from ortho-toluidine and also from benzylamine. The final product, i. e., at the end of the oxypropylation step, was a somewhat viscous, reddishcolored fluid. This was characteristic of all the various products obtained from the three amines. These products were, of course, slightly alkaline due to the residual caustic soda and also due to the basic nitrogen atom which is significant, at least in the case of benzylamine. The residual basicity due to the catalyst would, of course, be the same if sodium methylate had been used.

Speaking of insolubility in water or solubility in kerosene such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds. This is indicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molecular weight calculated by usual methods on basis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds with a high degree of accuracy when the molecular weights exceed 2,000. In some instances the acetyl value or hydroxyl value serves as satisfactorily as an index to the molecular weight as any other procedure, subject to the above limitations, and especially in the higher molecular weight range. If any difiiculty is encountered in the manufacture of the esters as described in Part 2 the stoichiometrical amount of acid or acid compound should ever, for purpose of economy it is customary to use either the acid or the anhydridc. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950 to De Groote and Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as para-toluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange oxypropylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such as diglycollic acid, which is strongly acidic there is no need to add any catalyst. The use of hydrochloric gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be pres cut. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever and to msure complete dryness of the diol as described in the final procedure just preceding Table 2.

The products obtained in Part 1 preceding may contain a basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part 1 is then diluted further with sufficient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 45% solution. To this solution there is added a polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycollic acid, etc. The mixture is refluxed until esterification is complete as indicated by elimination of Water or drop in carboxyl value. Needless to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However. if it is obtained from diglycollic acid, for example. water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example. the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (suflicient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear somewhat viscous straw-colored amber liquid so obtained may contain a small amount of sodium sulfate or sodium chloride but, in any event, is perfectly acceptable for esterification in the manner described.

It is to be pointed out that the products here described I are not polyesters in the sense there is a plurality of both diol radicals and acid radicals; the product is characterized by having only one diol radical.

In some instances and, in fact, in many instances 1 have found that in spite of the dehydration methods employed above that a mere trace of water still comes through and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification. particularly where there is no sulfonic acid or hydrochloric acid present as a catalyst. Therefore, I have preferred to use the following procedure: I have employed about 200 grams of the diol as described in Part 1, preceding; I have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150 C. When all this water or moisture has been removed I also Withdraw approximately 20 grams or a little less benzene and then add the required amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and, as far as solvent effect act as if they were almost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following:

I. B. P., 142 C. ml., 242 C. 5 ml., 200 C. ml., 244 C. 10 ml., 209 C. ml., 248 C. 15 ml., 215 C. ml., 252 C. 20 ml., 216 C. ml., 252 C. 25 ml., 220 C. ml., 260 C. 30 ml., 225 C. ml., 264 C. 35 ml., 230' C. ml., 270 C. 40 ml., 234 C. ml., 280 C. 45 ml., 237 C. ml., 307 C.

, in the manner previously described.

After this material is added, refluxing is continued, and, of course, is at a high temperature, to Wit, about to C. If the carboxy reactant is an anhydride needless to say no Water of reaction appears; if the carboxy reactant is an acid Water of reaction should appear and should be eliminated at the above reaction temperature. If it is not eliminated I simply separate out another 10 or 20 cc. of benzene by means of the phase-separating trap and thus raise the temperature to or C., or even to 200 C., if need be. My preference is not to go above about 200 C.

The use of such solvent is extremely satisfactory provided one does not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purpose such as demulsification the solvent might just as well be allowed to remain. If the solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling aromatic petroleum solvent might Well be replaced by some more expensive solvent, such as decalin or an alkylated decalin which has a rather definite or close range boiling point. The removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

In the appended table Solvent #7-3, which appears in all instances, is a mixture of 7 volumes of the aromatic petroleum solvent previously described and 3 volumes of benzene. This was used, or a similar mixture, In a large number of similar examples decalin has been used but it is my preference to use the above mentioned mixture and particularly with the preliminary step of removing all the Water. If one does not intend to remove the solvent my preference is to use the petroleum solvent-benzene mixture although obviously any of the other mixtures, such as decalin and xylene, can be employed.

The data included in the subsequent tables, i. e., Tables 2 and 3, are self-explanatory, and very complete and it is believed no further elaboration is necessary.

TABLE 2 Theo. M01. wt. Amt. of Ex. of Ex. No. of Theo. Actual Amt. of

acid hydroxy M. W(.J of 3??? l hydll oxyl 333 3 hyd. empd. Polyearboxy reactant ag 8 92;; ester cmpd. H. va ue 05 mm (gm) 1, 305 85. 8 87. 8 1, 276 197 Maleic anhydride... 30. 2 1, 305 85. 8 87. 8 1, 276 197 Diglyeollic acid. 42. 9 1,305 85. 8 87. 8 1, 276 197 Aconitlc acid. 53. 5 1, 305 85. 8 87. 8 1, 276 197 Citracoinic aei 34. 5 1, 740 64. 4 70. 2 1, 596 201 Diglycollic acid- 33. 8 1,740 64. 4 70. 2 1, 596 201 Maleic anhydride. 24. 3 1, 740 64. 4 70. 2 1, 596 201 Aconitie acid 43. 8 1, 740 64. 4 70. 2 1, 596 201 Citraconie acid 28. 0 2, 515 44. 6 64. 2 1, 744 198 Diglycollic acid 27. 9 2, 515 44. 6 64. 2 l, 744 201 Maleie anhydride... 23. 0 2, 515 44. 6 64. 2 1, 744 198 Aconitic acid 40. 7 2, 515 44. 6 64. 2 1, 744 199 25. 5 3, 820 29. 3 50. 8 2, 208 199 24. 1 3, 820 29. 3 50. 8 l 2, 208 198 26. 6 3, 820 29. 3 50. 8 2, 208 198 17. 7 3, 820 29. 3 50. 8 2, 208 199 Aconitie acid- 31. 0 3,820 29. 3 50. 8 2, 208 200 Oitraconic acid 20. 2 4, 560 24. 6 49. 2 2, 270 198 Diglycollie acid. 23. 4 4, 560 24. 6 49. 2 2, 270 199 Phthalio anhydride 25. 9 4, 560 24. 6 49. 2 2, 270 199 Maleic anhydride 1 7. 2 4, 560 24. 6 49. 2 2, 270 1 98 Aconitie acid 30. 4 4, 560 24. 6 49. 2 2, 270 199 Oitraconic acid 19. 6

TABLE 3 Ex. No. Amt. Esterifica- Time of of acid Solvent solvent tion temp, esterifieags; ut

ester (grs.) 0. tion (hrs) 227 140 4% None 241 188 4 5. 9 247 175 1 5. 4 235 164 None 230 173 3 4. 5 222 138 5% None 244 157 1 A 4. 5 227 140 5% None 227 168 3 4. 5 221 198 8 1. 1 235 157 2 4. 4 225 160 5 N one 220 188 3 2 3. 3 225 143 8% None 217 147 8 None 224 178 1 3. 4 220 1 78 5 /1 N one 218 166 7 3. 0 226 157 6 ,6 None 216 1 60 5 l4 0. 3 226 167 2 3. 3 219 159 3/; None The procedure for manufacturing the esters has been illustrated by preceding examples. If for any reason re action does not take place in a manner that is acceptable, attention should be directed to the following details: (a) Recheck the hydroxyl or acetyl value of the oxypropylated primary amines of the kind specified and use a stoichiometrically equivalent amount of acid; (b) if the reaction does not proceed with reasonable speed either raise the temperature indicated or else extend the period of time up to 12 or 16 hours if need be; (c) if necessary, use /f of paratoluene sulfonic acid or some other acid as a catalyst; (d) if the esterification does not produce a clear product a check should be made to see if an inorganic salt such as sodium chloride or sodium sulfate is not precipitating out. Such salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal as the size of the molecular increases the reactive h"- droxyl radical represents a smaller fraction of the entire molecular and thus more difficulty is involved in obtaining complete esterification.

Even under the most carefully controlled conditions of oxypropylation involving comparatively low temperatures and long time of reaction there are formed certain compounds whose composition is still obscure. Such side reaction products can contribute a substantial proportion of the final cogeneric reaction mixture. Various suggestions have been made as to the nature of these com pounds, such as being cyclic polymers of propylene oxide, dehydration products with the appearance of a vinyl radical, or isomers of propylene oxide or derivatives thereof, i. e., of an aldehyde, ketone, or allyl alcohol. In some instances an attempt to react the stoichiometric amount of a polycarboxy acid with the oxypropylated de rivative results in an excess of the carboxylated reactant for the reason that apparently under conditions of reaction less reactive hydroxyl radicals are present than indicated by the hydroxyl value. Under such circumstances there is simply a residue of the carboxylic reactant which can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced ratio of carboxylic reactant.

Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale reddish amber to reddish amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or the like color is not a factor and decolorization is not justified.

In the above instances I have permitted the solvents n to remain present in the final reaction mass. In other instances I have followed the same procedure using decalin or a mixture of decalin or benzene in the same manner and ultimately removed all the solvents by vacuum distillation. Appearances of the final products are much the same as the diols before esterification and in some 1nstances were somewhat darker 1n color and had a more reddish cast and perhaps somewhat more vlscous.

PART 3 Diols (nitrogen-free compounds) such as polypropylene glycol of approximately 2,000 molecular weight, for example, have been esterified with dicarboxy acids and employed as demulsilying agents. The herein described compounds are different from such diols although both, it is true, are high molecular weight dihydroxylated compounds. The instant compounds have present a nitrogen atom which is at least somewhat basic in the case of aniline or a comparable compound having a methyl group in the benzene ring. When derived from benzylamine such compounds have an unquestionably basic nitrogen atom present. In any event, even a nitrogen atom of low basicity probably influences the orientation of acidic molecules at interfaces. Stated another way, the ultimate ester has at least two free carboxyl radicals. It seems reasonable to assume that the orientation of such molecules at an oil-water interface, for example, are affected by the presence of a nitrogen atom having significant or definite basicity. Regardless of what the difference may be the fact still remains that the compounds of the kind herein described may be, and frequently are, 10%, 15% or 20% better on a quantitative basis than the simpler compound previously described, and demulsify faster and give cleaner oil in many instances. The method of making such comparative tests has been described in a booklet entitled Treating Oil Field Emulsions, used in the Vocational Training Course, Petroleum Industry Series, of the American Petroleum Institute.

it may be well to emphasize also the fact that oxypropylation does not produce a single compound but a cogeneric mixture. The factor involved is the same as appears if one were oxypropylating a monohydric alcohol or a glycol. Momentarily, one may consider the structure of a polypropylene glycol, such as polypropylene glycol of 2000 molecular weight. Propylene glycol has a primary alcohol radical and a secondary alcohol radical. In this sense the building unit which forms polypropylene glycols is not symmetrical. Obviously, then, polypropylene glycols can be obtained, at least theoretically, in which two secondary alcohol groups are united or a secondary alcohol group is united to a primary alcohol group, etherization being involved, of course, in each instance.

Usually no effort is made to differentiate between oxypropylation taking place, for example, at the primary alcohol unit radical or the secondary alcohol radical. Actually, when such products are obtained, such as a high molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such as HO(RO)nH in which n has one and only one value, for instance, l4, 15 or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture. On a statistical basis, of course, 11 can be appropriately specified.

PART 4 Previous reference has been made to other oxyalkylating agents other than propylene oxide, such as ethylene oxide. Obviously variants can be prepared which do not depart from what is said herein but do produce modifications. Aniline or other suitable primary amine can be reacted with ethylene oxide in modest amounts and then subjected to oxypropylation provided that the resultant derivative is (a) water-insoluble, (b) kerosenesoluble, and (c) has present 15 to alkylene oxide radicals. Needless to say, in order to have water-insolubility and kerosene-solubility the large majority must be propylene oxide. Other variants suggest themselves as, for example, replacing propylene oxide by butylene oxide.

More specifically, one mole of aniline can be treated with 2, 4 or 6 moles of ethylene oxide and then treated with propylene oxide so as to produce a water-insoluble, kerosene-soluble oxyalkylated aniline in which there are present 15 to 80 oxide radicals as previously specified. Similarly the propylene oxide can be added first and then the ethylene oxide, or random oxyalkylation can be employed using a mixture of the two oxides. The compounds so obtained are readily esterified in the same manner as described in Part 2, preceding. Incidentally, the diols described in Part 1 or the modifications described therein can be treated with various reactants such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or monochloroacetic acid the resultant product can be further reacted with a tertiary amine such as pyridine, or the like, to give quaternary ammonium compounds. If. treated with maleic anhydride to give a total ester the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulto groups can be introduced also by means of a sulfating agent as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite.

I have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties of the original hydroxylated compound insofar that they are effective and valuable demulsifying agents for resolution of water-in-oil emulsions as found in the petroleum industry, as break inducers in doctor treatment of sour crude, etc.

This application is a continuation-in-part of my copending application Serial No. 183,294, filed September 5, 1950, and now abandoned.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is

l. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

(H0oC)1|"R (OHUCfl)n N*-(CBHGO)IH%R(C0OH)1|" t,

in which R is a hydrocarbon radical selected from the group consisting of phenyl radicals, methylphenyl radicals, and benzyl radicals, and n and n are whole numbers with the proviso that it plus 11 equals a sum varying from to 80; n is a whole number not over 2 and R is the radical of a polycarboxy acid selected from the group consisting of acyclic and isocyclic polycarboxy acids having not more than 8 carbon atoms and composed of carbon, hydrogen and oxygen of the formula:

COOH

(COOHM in which n" has its previous significance with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble and kerosene-soluble.

2. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which R is a hydrocarbon radical selected from the group consisting of phenyl radicals, methylphenyl radicals, and benzyl radicals, and n and n are whole numbers with the proviso that it plus 11 equals a sum varying from 15 to and R is the radical of a dicarboxy acid selected from the group consisting of acyclic and isocyclic dicarboxy acids having not more than 8 carbon atoms and composed of carbon, hydrogen and oxygen of the formula:

COOH

COOH

with the further proviso that the parent dihydroxy compound prior to esterification be water-insoluble and kerosene-soluble.

3. Hydrophile synthetic products; said hydrophile syntheltic products being characterized by the following ormu a:

in which n and rz are whole numbers with the proviso that 11 plus it equals a sum varying from 15 to 80; and R is the radical of a dicarboxy acid selected from the group consisting of acyclic and isocyclic dicarboxy acids having not more than 8 carbon atoms and composed of carbon, hydrogen and oxygen of the formula:

COOH

GOOH

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,442,075 De Groote et al May 25, 1948 2,442,076 De Groote et al May 25, 1948 2,442,077 De Groote et a1 May 25, 1948 2,562,878 Blair Aug. 7, 1951 

1. HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA: 